Degradable hydrocarbon polymers

ABSTRACT

A DEGRADABLE COMPOSITION IS MADE FROM A POLYMER OF A MONO OLEFIN HAVING 2-3 CARBON ATOMS OR STYRENE AND AN ADDITIVE COMPRISING (1) A DERIVATIVE OF AN ORGANIC COMPOUND OF A METAL WHICH HAS AT LEAST TWO VALENCE STATES AND (2) A BENZOYL DERIVATIVES OF AN ORGANIC COMPOUND OR A TRIAZOLE.

Aug. 20, 1974 D. E. HUDGIN ETAL DEGRADABLE HYDROCARBON POLYMERS Filed' July e, 1972 XQ, z 5. 4 5. 2 l o 0 O O. O.

United States Patent O 3,830,764 DEGRADABLE HYDROCARBON POLYMERS Donald E. Hudgn, Princeton Junction, and Thomas Zawadzki, Princeton, NJ., assignors to Princeton Polymer Laboratories, Inc., Princeton, NJ.

Filed July 6, 1972, Ser. No. 269,291 Int. Cl. C08f 45/00 U.S. Cl. 260-23 H 32 Claims ABSTRACT OF THE DISCLOSURE A degradable composition is made from a polymer of a mono olefin having 2-3 carbon atoms or styrene and Ian additive comprising (1) a derivative of an organic compound of a metal which has at least two valence states and (2) a benzoyl derivative of an organic compound or a triazole.

'I`his invention relates to a new polymer composition, based on polystyrene, polypropylene, polyethylene or ethylenepropylene copolymer and a novel additive system, which has predictable degradability when exposed to sunlight and air.

It is known that unstabilized polymers of propylene, styrene and ethylene will slowly degrade outdoors in presence of air and sunlight. Furthermore, it is known that certain additives will enhance this degradation, e.g. see Newland Pat. 3,592,792, Moore Pat. 3,320,695 and Newland fPat. 3,454,510. None of these additives, however, have proved to be satisfactory because the rate of degradation is still much too slow to cause the polymer to degrade within a reasonable length of time or the cost is too high to be economically feasible.

It is extremely important today to find an effective means of destroying plastic materials, which are used in packaging and agricultural mulch films. The pollution problem is becoming more severe as used plastic bottles, containers, wrapping iilm, sheet, etc. accumulate in garbage dumps, along shores, in rivers and other places. There is a great need for some sort of degrading system that will allow the plastic to have a useful life, after which the plastic will degrade into a material that can be handled easily.

This invention provides a new Apolymeric `system capable of degrading to a crumbly friable mass in a matter of hours when exposed to sunlight and air. The rate of degradation can be controlled such that the degradation in sunlight and air can be made to happen at any time from a few hours to a few months. This can be done primarily by controlling the amount of additive system incorporated in the polymer and by the method of incorporation.

In the course of our study on additives to bring about degradation of polymers, two types of additives were combined. An unexpected synergism resulted giving amazingly fast degradation rates. Although the precise mechanism is not known, it appears highly probable that the two components of the additive system degrade the polymer by different mechanisms and that the breakdown products produced by the effect of one component becomes very vulnerable for attack by the second component.

As the polymer there is employed a polymer of a mono oletin having 2 to 3 carbon atoms, i.e. polyethylene, polypropylene, ethylene-propylene copolymer (eg. ethylene and propylene in a mole ratio of 5:95, 25:75, 50:50, 75 :25 or 95:5) or polystyrene.

Any of the conventional polyethylenes can be used, i.e. low,medium or high density, e.g. density of 0.914 to 0.96, for example polyethylene having a density of 0.918 and a melt index of 1.7, polyethylene of density of 0.945, polyethylene of density 0.925, or polypropylene having a bire- 3,830,764 Patented Aug'. 20, 1974 lCC fringent melting point of about 168C. and a :reduced specific viscosity of 2.5 (measured on a 0.1% solution in decahydronaphthalene at C.).

Typical examples of polyethylene, polypropylene, ethylenepropylene copolymers and polystyrene are set forth in the Encyclopedia of Polymer Science, Vol. 6, pages 275-386, Vol. ll, pages 597-619 and Vol. 13, pages 156-439, the entire disclosure of which `are hereby incorporated by reference.

The additive system is composed of two components which we will call P and S for convenience.

P is a metallic derivative, derived from a transition metal capable of existing in two or more valence states. Examples of such metals are iron, cobalt, nickel, chromium, titanium, vanadium, manganese, copper, zirconium, tin and antimony. These metals may be in the form of metal salts or organic acids, such as cycloalkanoic acids, alkanoic acids, hydroxyalkanoic acids, haloalkanoic acids, alkenoic acids, aryl carboxylic acids, haloaryl carboxylic acids, e.g. formic acid, acetic acid, propionic acid, butyric acid, isobu'tyric acid, valerio acid, caproic acid, caprylic acid, trimethylacetic acid, pelargonic acid, decanoic acid, lauric acid, palmitic acid, stearic acid, eicosanic acid, oleic acid, linoleic acid, palmitoleic acid, acrylic acid, glycolic acid, lactic acid, citric acid, tartaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, tricarbyllic acid, uoroacetic acid, chloroacetic acid, bromoacetic acid, dichloroacetic acid, alpha-chloropropionic acid, beta-chloropropionic acid, saccharic acid, phenylacetic acid, benzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-chlorobenzoic acid, m-bromobenzoic acid, terephthalic acid, phthalic acid, neodecanoic acid.

Examples of such salts include zirconium IV neodecanoate, zirconium II neodecanoate, zirconium IX oxalate, triglycolatozirconylic acid, zirconyl acetate, trilactozirconylic acid, zirconium IV stearate, zirconium IV octoate, zirconium IV palmitate, zirconium IV oleate, stannous acetate, stannic acetate, stannous neodecanoate, stannous formate, stannous stearate, stannous oxalate, titanium oxalate, titanium IV neodecanoate, titanium IV stearate, stannous 2-ethylhexoate, nickelous acetate, nickelous formate, nickel II naphthenate, nickel II oleate, nickel II stearate, nickel II oxalate, nickel II formate, nickel l1 acetate, manganous acetate, manganous lactate, manganous oxalate, manganous tartarte, manganous benzoate, manganic acetate, ferrous acetate, ferrie acetate, ferrous formate, ferrie formate, ferrous lactate, ferric lactate, ferric malate, ferrie oleate, ferrous oxalate, ferric oxalate, ferrous citrate, ferrie citrate, ferrie benzoate, antimony lactate, cupric lactate, cupric acetate, cupric oleate, cupric stearate, cupric naphthenate, cupric formate, cobalt II oleate, cobalt II stearate, cobalt II naphthenate, cupric oxalate, cupric tartrate, cobaltous tartrate, cobaltous linoleate, cobaltous palmitate, cobaltous oxalate, cobaltous acetate, cobaltic acetate, manganous naphthente, iron naphthenate, manganous oleate, manganous linoleate, cobaltous linoleate, manganous octoate, iron resinate, cobaltous resinate, manganous resinate, manganous neodecanoate, cobalt II neodecanoate, chromic oleate, stannic oleate, chromous acetate, chromic acetate, chromic stearate, chromic naphthenate, cupric adipate, and litanium IV adipate, litanium IV phthalate.

There also can be formed complexes or chelates of the same metals with beta diketones such as 2,4-pentanedione (acetylacetone). Examples of such 2,4 pentanedione chelates include cobaltic pentanedione, ferrous pentanedione, ferric pentanedione, cupric pentanedione, titanium IV pentanedione, zirconium 1V pentanedione, stannous pentanedione, nickel II pentanedione, chromium III pentanedione, manganous pentanedione.

3 S is a benzoyl derivative, preferably having a ketone group or a benzotriazole derivative and is represented by the following structures:

Riz

Ria

where R11 thru R14 may be H, halogen, alkyl, aryl, alkoxy, aralkyl, aroyl or aryloxy group. In R1-R6 and R11-R1., the alkyl groups can have l to 20 carbon atoms as can the alkoxy groups.

Examples of benzoyl compounds are benzophenone, 4- chlorobenzophenone, 4,4' dimethoxybenzophenone, 4- fluorobenzophenone, 2-phenyl acetophenone, o-dibenzoyl benzene, 4-bromobenzophenone, 2,4,5-triethoxybenzophenone, 2,4,6 trimethoxy benzophenone, 4methoxybenzo phenone, 4 bromo-4'chlorobenzophenone, 4-methylbenzophenone, 4,4dichlorobenzophenone, phenyl benzoate, benzil, acetophenone, 4' chloroacetophenone, 4chloro butyrophenone, propiophenone, butyrophenone, 2-ch1oroacetophenone, 3chloroacetophenone, 2,4,6-trichl0roacetophenone, Z-methylbenzophenone, 3-ethylbenzophenone, 4- eicosanylbenzophenone, 4-octadecylbenzophenone, 4,4di octadecylbenzophenone, 4 ethoxybenzophenone, 4-octadecoxybenzophenone, 4-eicosanoxybenzophenone, 4-butoxybenzophenone, 4,4' dioctadecoxybenzophenone, 4,4-

'diethoxybenzophenone, benzyl phenyl ketone, 2-phenylbenzophenone, 4 phenylbenzophenone, 2pyridyl phenyl ketone, pyridyl 4-chlorophenyl ketone, 2-chloro-4-methyl benzophenone, 3 benzoyl acetophenone, chloromethyl phenyl ketone, 4,4dimethylbenzophenone, 4,4diphen oxy benzophenone, S-phenoxybenzophenone, phenyl 1- naphthyl ketone, 2' acetonaphthone and 1'acetonaph thone, phenyl 4-chlorobenzoate, phenyl 3-methylbenzoate, phenyl 4-dodecylbenzoate, phenyl 2-bromobenzoate, phenyl 3-uorobenzoate, phenyl 2,4-dimethylbenzoate, phenyl 2 methyl-4-bromobenzoate, phenyl 2,4,5-trichlorobenzo ate, phenyl Z-methoxybenzoate, phenyl 4-but0xybenzoate, phenyl 4-phenoxybenzoate, methyl benzoate, ethyl benzoate, sec. butyl benzoate, octadecyl benzoate, eicosanyl benzoate, 4-chloropheny1 benzoate, 3-methylphenyl benzoate, 4octylphenyl benzoate, 4-octadecylphenyl 4'chloro benzoate, 4-methoxyphenyl benzoate.

Examples of benzotriazole derivatives include benzotriazole, 5 chlorobenzotriazole, 5 bromobenzotriazole, 5- fluorobenzotriazole, S-methylbenzotriazole, 5,7-dimethylbenzotriazole, S-methoxybenzotriazole, S-ethoxybenzotriazole, 5 octadecoxybenzotriazole, 5 octadecylbenzotriazole, 5 methyl-7-chlorobenzotriazole, -methylbenzotriazole, 5,6-dimethyl-8chlorobenzotriazole, S-benzylbenzotriazole, 7-phenoxybenzotriazole, 5-benzoyl benzotriazole.

Different methods of incorporation of the additives have been used effectively. In relatively thin plastic forms such as sheets and films the additive may be incorporated by merely dipping the plastic into a solution of the additive for a short time (eg. a few seconds). For thicker plastic parts the additive can be incorporated effectively by normal processing techniques similar to lthe way other additives such as fillers are incorporated. This may be done on a roll mill, Banbury or extruder effectively. This latter method is preferred even for film and bottles because of uniformity and control of level of additive incorporated.

A special method that has many practical uses is a spray-on technique. This is useful on trash heaps where large quantities of used plastic articles have accumulated. Rather than burning the plastic, it could be sprayed on easily and quickly With a solution of the additives in any volatile solvent and in a few days the useless plastic will have virtually disappeared. This can solve a major pollution problem.

Based on the total of the polymer and the additives the polymer is normally 99.999% and the additive is 0.00l-l0% usually being present in an amount of at least 0.01%. The P and S components of the additive can be present in equal amounts or either one can fbe excess, e.g. the additive can be 5 to 95% P and 95 to 5% S. Usually it is preferred to have the S component as the larger component. As is shown in example 1 as little as 0.1 p.p.m. of additive is effective in disintegrating the polymer.

Unless otherwise indicated all parts and percentages are by weight.

The compositions of the present invention degrade very rapidly under a sunlamp but do not degrade rapidly under a regular fluorescent lamp. The compositions degrade under the influence of ultra violet light more rapidly than when the polymer is present with no additive or with only one additive.

Direct incorporation of the additives into the polymer by compounding on a roll mill or through a compounding extruder gives exact levels of the additives. In the dip technique the amount of each additive incorporated in the specimen (film or sheet) was determined by subjecting the specimen to analysis.

A 11/2 mil polyethylene film was dipped for l0 seconds in the following solution at 60 C.:

After dipping the film was dried and analyzed. The following analyses were reported:

Percent This corresponds to the following percentages of the original additives:

Percent Zr Neodecanoate 0.43 4-Chlorobenzophenone 0.085

Thus only very small amounts are needed to be effective.

The controllability and predictability of the degradation of the polymer composition can be important. In the case of agricultural mulch films, exposure times to degradation must be precise so that new growing plants under the film can break through the film at the right time and thus assure strong healthy growth for the plants. In other areas, such as plastic bottles, the precision of the time for degradation may not be so critical. Still, within limits, some degree of accuracy is desirable. Our studies have allowed us to correlate light exposure time to degradation with amount and type of additives used. These studies have involved both sunlamp continuous exposure as well as outdoor sunlight exposure. In the sunlamp exposures the sunlamp was run 24 hours a day.

Samples of film (l to 5 mils) and sheet (5-50 mils) were exposed by mounting a l x 3 specimen in clamps on a holder so that it was suspended about 1A" above the surface. Each specimen thus mounted was placed on an 18 diameter horizontal round table, which was rotated at 33 r.p.m. Above the table at approximately 11 inches were 4 General Electric RS sunlamps. All of this equipment was housed in a metal box approximately 2l wide, 2l deep and 24 high. On opposite sides of the boxes at the turntable level were two openings l7" wide by 7" high. A fan of adjustable speed was used to blow through the openings to control the turntable temperature (37 i2 C.).

The light intensity was checked periodically to make sure that it remained fairly constant. When a drop in intensity was observed, new sunlamps were used to replace the used lamps.

The specimens were periodically tested by applying pressure on the suspended -lm or sheet. A specimen was considered to have failed when it broke on application of a slight pressure (zero elongation).

The sunlamp exposures were also correlated with tests in outdoor sunlight.

During the months from April through September an outdoor rack was used to expose samples of polymer lm and sheet. These samples were mounted in holders similar to those used for sunlamp exposure as previously described. The rack faced South and was set at a 45 angle to the horizontal. Although outdoor sunlight intensity is variable depending on haze, clouds and rain, over a period of time reasonably good correlation was obtained as shown by typical examples in the following Table:

TABLE I lme to failure (days) Sample Sun lamps Outdoor The examples that follow are submitted to illustrate and not to limit this invention.

EXAMPLE 1 Commercial crystal grade polystyrene was compounded with the following ingredients on a roll mill to give mixtures with diierent levels of additive:

l part of Zirconium Neodecanoate 5 parts of o-Dibenzoyl Benzene EXAMPLE 2 Commercial polypropylene iilm specimens (1 x 3" x .0015") were dipped in the following chloroform solutions at C. for 2 seconds, washed in fresh chloroform for 2 seconds and dried at room temperature.

Soln. 1: Ferrous Pentanedione (2%) Soln. 2: 4-Methyl Benzophenone (2%) Soln. 3: A 1 to 5 mixture of Solns. 1 and 2 (i.e. a mixture of l0 ml. of solution 1 with 50 ml. of solution 2 was used) The treated polypropylene film specimens were mounted in film holders and exposed to 4 GE sunlamps on a revolving table. The Iilm specimens were tested periodically. When a ilm broke under slight pressure, this was taken as the time of failure. For the described specimens the following results were obtained:

Dip Soln.: Hours to Failure Soln. 1 210 Soln. 2 160 Soln. 3 Less than 16 Examples 3 and 4 also show the synergistic effect. Except for the additives, treatment of the film' was the same as described in Example 2 using a chloroform solution of the additives.

Hourr to Example Film used Components failure 3 1% mil poly- Titanium (+4) pentanedione 200 styrene.

4ethoxybenzopl1enone. 185 1-5 ratio of above components-.- 16

4 1% mil poly- Co pentanedione 114 propylene.

4-bro1nobenzophenone 170 1-5 ratio of above components.-- 16 In the following examples the chloroform solution contained equal parts of components A and B:

1.5 mil low density (about 0.916) ploly so t ethylene film, 10 sec. dip in CHOI:

Time to failure (hrs. exposure) Component Componentl Mixture of Example Component A Component B one alone A and B 5 Zirconium Il neodecanoate 4-chlorobenzophenone 234 214 14 6 Cobalt plus 2 neodecanoate do 311 214 118 7.. Ferrie pentanedinne dn 480 214 92 8.. Ti plus 4 pentanedione 2-phenylaeetophenone 94 433 44 9.. Ferrous pentanedione... .do 281 433 44 10. Cobalt III pentanedione. 4chlorobenzophenone 311 214 85 11. do 2-phenylacetophenone. 311 236 42 12 Zirconium plus 2 neodecanoate. do 234 236 109 13. Ferrous pentanedione 4-chlorobenzophenone.. 281 214 21 14 Titanium lV pentanedione do 94 214 21 15 .do 2-phenylacetophenone. 94 236 21 16. Fen-ons pentanediene. Benzophenone 281 236 42 17 .do 4-methylbenzophenone 281 165 76 18 do 4-bromobenzophenone. 281 236 47 19 dn 4-uorobenzophenone 281 207 76 2n dn 4,4diehlorobenzophenone 281 165 47 21 .do.. Phenyl benzoate 281 214 49 do 2,4,5-triethoxybenzophenon 281 424 243 do 2,4,6-tnmethoxybenzophenon 281 424 214 do 4-methoxybenzophenone 281 207 95 do.. 5-ehlorobenzotriazele 281 214 139 dn Acetophenone 281 214 91 Ferrie napthenate. 4-chlorobenzopheno 706 214 49 Ferrous pentanedlo 4chloroacetophenone 281 214 91 Ferrous stearato Benzophenone. 236 98 Ferrous octoate-. 4-chlorobenzopheno 400 214 96 3l.- Ferrous neodeeanoate.. do 141 214 96 32 Ferrous pentanedione o-Dibenzoylbenzene.. 281 (l) 95 33 do 2acetonaphthone 281 (l) 84 34 dn 1avetnnanhfhnm= 281 (l) 133 35 do Benzil 281 (l) 65 36 do Phenyl 2-pyridy1 ketone 281 (1) 36 1 Not determined.

What is claimed is:

1. A polymeric composition having a controllable degradation rate in sunlight and air comprising (1) a polymer which is selected from the group consisting of polymer of an olen having 2 to 3 carbon atoms and (2) a two component additive system, the first component of said additive lbeing a salt of an organic carboxylic acid with a metal capable of existing in at least two valence states and the second component of the additive being selected from the group consisting of ('a) a benzoyl compound of the formula:

and (b) acetonaphthone where R1, R2, R3, R4, and R are selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, aryloxy, benzoyl and aryl, and R5 is selected from the group consisting of alkyl, aralkyl, aryl, and pyridyl groups and such groups substituted with a substituent from the group consisting of halogen, alkyl, aryl, alkoxy, and aryloxy and said additive system being present in an amount effective to decrease the time of degradation of the polymer under the influence of ultraviolet light, each of said components of the additive system being present in an amount sufficient .that the mixture thereof is more effective to decrease the time of degradation of the polymer than a corresponding amount of either member of the two component additive system by itself.

2. A polymer composition according to claim 1 wherein the metal of the first component is selected from the group consisting of iron, cobalt, nickel, chromium, titanium, vanadium, manganese, copper, zirconium and tin.

3. A polymeric composition according to claim 1 wherein the organic carboxylic acid is free of non hydrocarbon substituents.

4. A polymeric composition according to claim 3 wherein at least two of R1, R2, R3, R4 and \R5 are hydrogen and the rest are selected from the group consisting of hydrogen, lower alkyl, halogen, lower alfkoxy, benzoyl and phenyl 'and R6 is selected from the group consisting of lower alkyl, phenyl, and halophenyl.

5. A polymeric composition having a controllable degradation rate in sunlight and air comprising (l) a polymer which is a member of the group consisting of polymer of an oletin having 2 to 3 carbon atoms and styrene polymers and (2) a two component additive system, the iirst component of said additive being a salt of an organic carboxylic acid with a metal capable of existing in at least two valence states, and the second component of the additive being selected from the group consisting of (a) a benzoyl compound of the formula:

R1 O ll C-Rg and (b) acetonaphthone where R1, R2, R3, R4, and R5 are selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, aryloxy, benzoyl and aryl, and R3 is selected from the group consisting of alkyl, aralkyl, aryl, and pyridyl groups and such groups substituted with a substituent from the group consisting of halogen, alkyl, aryl, alkoxy, Iand aryloxy, said additive system being present in au amount effective to decrease the time of degradation of the polymer under the inuence of ultraviolet light, each of said components of the additive system being present in an amount sufficient that the mixture thereof is more effective to decrease the time of degradation of the polymer than a corresponding amount of either member of the two component additive system by itself.

6. A polymer composition according to claim 5 wherein the metal of the iirst component is selected from the group consisting of iron, cobalt, nickel, chromium, titanium, vanadium, manganese, copper, zirconium and tin.

7. A polymeric composition according to claim 6 wherein the second component of the additive system is (a).

8. A polymeric composition according to claim 7 wherein the organic carboxylic acid is free of non hydrocarbon substituents.

9. A polymeric composition according to claim 8 wherein at least two of R1, R2, R3, R4 and R5 are hydrogen and the rest are selected 4from the group consisting of hydrogen, lower alkyl, halogen, lower alkoxy, benzoyl and phenyl and R6 is selected from the group consisting of lower alkyl, phenyl, and halophenyl.

10. A polymeric composition according to claim 9 wherein the second component of the additive is a monoketone and R3 is lower alkyl, phenyl, or halophenyl.

11. A composition according to claim 10 wherein the two component additive system is present in an amount of at least 1 p.p.m. of the polymer.

12. A composition according to claim 11 wherein each component of the additive system is present in an amount of 5 to 95% of the additive system.

13. A composition according to claim 6 wherein the polymer is polyethylene, the two component additive system is present in an amount of 0.001-l0% of the total of polymer and additive system and each component of the additive system is present in an amount of 5 to 95% of the additive system.

14. A composition according to claim 6 wherein the polymer is polypropylene, the two component additive system is present in an amount of 0.00l-l0% of the total of polymer and additive system and each component of the additive system is present in an amount of 5 to 95% of the additive system.

15. A composition according to claim 6 wherein the polymer is polystyrene, the two component additive system is present in an amount of 1 p.p.m. of the polymer up to 10% of the total of polymer and additive system and each component of the additive system is present in an amount of 5 to 95 ofthe additive system.

16. A composition according to claim 9 wherein the second component of the additive is o-dibenzoyl benzene.

17. A composition according to claim 5 wherein the 2- component additive system is present in an amount of at least l p.p.m. of the polymer.

18. A composition comprising a rst component which is a salt of an organic carboxylic acid with a metal capa- Ible of existing in at least two valence states, and a second component selected from the group consisting of (a) a benzoyl compound of the formula:

Rn R1 0 R3 -C-R.

and (b) acetonaphthone where R1, R2, R3, R4 and R5 are selected from the group consisting of hydrogen, halogen, alkyl, alkoxy, aryl, and aryloxy and R6 is selected from the group consisting of alkyl, aralkyl, aryl, and pyridyl groups and such groups substituted with a member of the group consisting of halogen, alkyl, aryl, alkoxy, and aryloxy, each of said components being present in an amount suflicient that the mixture thereof is more effective to decrease the time of degradation of a polymer of an olefin having 2 to 3 carbon atoms than a corresponding amount of either member of the two component additive system by itself.

19. A composition according to claim 18 wherein the metal of the rst component is selected from the group consisting of iron, cobalt, nickel, chromium, titanium, vanadium, manganese, copper, zirconium and tin.

20. A composition according to claim 19 wherein the organic carboxylic acid is free of non hydrocarbon substituents.

y and (b) acetonaphthone where R1, R2, R3, R4 and R5 are selected from the group consisting of hydrogen, halogen, alkyl, benzoyl, alkoxy, aryl, and aryloXy and R6 is selected from the group consisting of alkyl, aralkyl, aryl, and pyridyl groups and such groups substituted with a member of the group consisting of halogen, alkyl, aryl, alkoxy, and aryloxy, each of said components being present in an amount sufcient that the mixture thereof is more effective to decrease the time of degradation of a polymer of an olen having 2 to 3 carbon atoms than a corresponding amount of either member of the two component additive system by itself.

22. A composition according to claim 21 wherein the metal of the first component is selected from the group consisting of iron, cobalt, nickel, chromium, titanium, vanadium, manganese, copper, zirconium and tin.

23. A composition according to claim 22 wherein the second component is (a).

24. A composition according to claim 23 wherein the organic carboxylic acid is free of non hydrocarbon substituents.

25. A composition according to claim 24 wherein at least Itwo of R1, R2, R3, 'R4 and R5 are hydrogen and the rest are selected from the group consisting of hydrogen, lower alkyl, halogen, lower alkoxy, benzoyl and phenyl and R6 is selected from the group consisting of lower a1- kyl, phenyl, and halophenyl.

26. A composition according to claim 21 wherein the second component is a mono ketone and R6 is lower alkyl, phenyl or halophenyl.

27. A composition according to claim 26 wherein each component is present in an amount of 5 to 95% of the total of the two components.

28. A composition according to claim 26 wherein the metal is iron.

29. A composition according to claim 26 wherein the metal is cobalt.

39. A composition according to claim 26 wherein the metal is titanium.

31. A composition according to claim 26 wherein the metal is zirconium.

32. A composition according to claim 1 wherein the metal is titanium.

References Cited UNITED STATES PATENTS 3,454,510 7/ 1969 Newland ett al. 260--23 3,679,777 7/ 1972 Lambert 260-93.7

FOREIGN PATENTS 38,687 11/1971 Japan 260-94.9

OTHER REFERENCES Chem. Abstracts, Vol. 68, p. 7665, 1958.

DONALD E. CZAJA, Primary Examiner E. C. RZUCIDLO, Assistant Examiner U.S. Cl. X.R.

220-Dig- 30, 23 S, 32.8 A, 93.5 R, 93.7, 94.9 GC, dig. 43

Notice of Adverse Decision in Interference In Interference No. 99,900, involving Patent No. 3,830,764, D. E. Hydgin and T. Zawadzki, DEGRADABLE HYDROCARBON POLYMERS, final judgment adverse to the patentees was rendered June 15, 1983, as to claims 5, 6, 15, 17, 18 and 19.

[Official Gazette'February 7, 1984.]

Disclaimer 3,830,764.Donald E. Hudgn, Princeton Junction and Thomas Zawadzk, Princeton, NJ. DEGRADABLE HYDROCARBON POLYMERS. Patent dated Aug. 20, 1974. Disclaimer filed June 10, 1983, by the assignee, Princeton Polymer Laboratories, Inc. Hereby enters this disclaimer` to claims 5, 6, 15, 17, 18 and 19 of said patent.

[Official Gazette July 26, 1983.] 

